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US3954658A - Oil-in-water emulsion and emulsifying or solubilizing composition therefor - Google Patents

Oil-in-water emulsion and emulsifying or solubilizing composition therefor Download PDF

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US3954658A
US3954658A US05/601,971 US60197175A US3954658A US 3954658 A US3954658 A US 3954658A US 60197175 A US60197175 A US 60197175A US 3954658 A US3954658 A US 3954658A
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Prior art keywords
oil
weight
composition
ingredient
fatty acid
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US05/601,971
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Hisao Tsutsumi
Junichi Kawano
Ikuya Kinoshita
Hirokazu Nakayama
Toshino Ukena
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Kao Corp
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Kao Soap Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4993Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017Mixtures of compounds
    • C09K23/018Mixtures of two or more different organic oxygen-containing compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06Protein or carboxylic compound containing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/905Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/917The agent contains organic compound containing oxygen
    • Y10S516/918The compound contains carboxylic acid ester group

Definitions

  • This invention relates to an emulsifying or solubilizing agent composition which is highly effective for emulsifying and solubilizing liquid vegetable oils and highly polar synthetic ester oils, the emulsification or solubilization of which has heretofore been regarded as being very difficult.
  • non-ionic surface active agents such as polyoxyethylene sorbitan-fatty acid esters, sorbitan-fatty acid esters, glycerol-fatty acid esters, polyethylene glycol-fatty acid esters and polyoxyethylenealkyl esters, but also a great variety of non-ionic, anionic, cationic and amphoteric surface active agents.
  • these emulsifiers have a good emulsifying activity to mineral oils composed of hydrocarbons and the like and animal oils such as squalane, and they provide stable emulsions of these oils.
  • these surface active agents can scarcely emulsify liquid vegetable oils composed of triglycerides full of aliphatic hydrocarbon groups having unsaturated bonds (hereinafter referred to merely as “vegetable oils”), such as camellia oil and olive oil, or esters having at least one branched alkyl group, which are synthesized from a branched or linear higher fatty acid and a branched or linear higher alcohol (hereinafter referred to merely as "synthetic ester oils”), and stable emulsions of these vegetable oils or synthetic ester oils have not been provided.
  • vegetable oils composed of triglycerides full of aliphatic hydrocarbon groups having unsaturated bonds
  • vegetable oils such as camellia oil and olive oil
  • esters having at least one branched alkyl group which are synthesized from a branched or linear higher fatty acid and a branched or linear higher alcohol
  • synthetic ester oils stable emulsions of these vegetable oils or synthetic ester oils have not been provided.
  • an emulsifying or solubilizing agent capable of readily emulsifying or solubilizing the aforesaid vegetable oils or synthetic ester oils to provide stable emulsions thereof.
  • a composition formed by incorporating specific amounts of a fatty acid alkali metal salt, a fatty acid and an oleic acid ester of a polyethylene glycol into a polyoxyethylene sorbitol-fatty acid ester type surface active agent.
  • an emulsifying or solubilizing agent composition comprising 58 to 95% by weight of a polyoxyethylene sorbitol-unsaturated fatty acid ester (hereinafter referred to as "component (I)") having the formula (A) ##EQU2## wherein the sum of n1 + n2 + n3 + n4 + n5 + n6 is from 10 to 60, and on the average up to 3 of the X's are hydrogen and the balance of the X's are linear unsaturated acyl groups having 18 carbon atoms,
  • component (II) an alkali metal salt of a linear saturated or olefinically unsaturated fatty acid having 12 to 18 carbon atoms
  • component (III) a linear saturated or olefinically unsaturated fatty acid having 12 to 18 carbon atoms
  • component (IV) a C 18 linear unsaturated fatty acid ester of a polyethylene glycol having an average molecular weight of 150 to 2,000
  • the aforesaid types of vegetable oils and synthetic ester oils which are highly polar emollient oils and have heretofore been regarded as being difficult to emulsify, can easily be emulsified or solubilized, and good, stable and ideal emulsions of these oils can be obtained.
  • These vegetable oils are liquid vegetable oils composed of triglycerides containing many unsaturated aliphatic hydrocarbon groups, such as camellia oil, olive oil, safflower oil, rapeseed oil, palm oil and cotton seed oil, and the synthetic ester oils are esters having at least one branched alkyl group, which are synthesized from branched or linear higher fatty acids and branched or linear higher alcohols.
  • synthetic ester oil there can be mentioned, for example, 2-heptylundecyl isostearate, glyceroltris-2-ethylhexanoate, hexadecyl-2-ethylhexanoate, hexadecyl isostearate and hexadecyl isotridecanoate.
  • These vegetable oils and synthetic ester oils are especially useful for cosmetics, and by the use of the composition of this invention, it is possible to employ these oils in the emulsified or solubilized state in cosmetics.
  • composition of this invention exhibits an excellent emulsifying effect not only to these vegetable oils and synthetic ester oils, but also to mineral oils and animal oils which can also be emulsified by conventional emulsifiers.
  • the polyoxyethylene sorbitol-unsaturated fatty acid ester used as the component (I) in this invention is obtained by partially or fully esterifying a sorbitol-ethylene oxide adduct with an unsaturated fatty acid having 18 carbon atoms, such as oleic acid.
  • an unsaturated fatty acid having 18 carbon atoms such as oleic acid.
  • the 6 hydroxyl groups of said adduct from 3 to 6 of such groups, on the average, are esterified.
  • from 3 to 6 of the X's are acyl groups and the remaining X's are hydrogen.
  • the degree of esterification When a compound having a lower degree of esterification outside the above range is employed, the emulsifying effect is diminished and good emulsions cannot be obtained. Further, the stability is reduced. Unsaturated fatty acids having 18 carbon atoms, preferably oleic acid and linoleic acid, are employed for this esterification.
  • RCO-- wherein R is an olefinically unsaturated acyclic unbranched hydrocarbon radical having 17 carbon atoms and having from one to 4 double bonds in the hydrocarbon chain.
  • saturated fatty acids such as stearic acid and palmitic acid are employed for esterifying the sorbitolethylene oxide adduct, the emulsifying effect of compositions containing such esters is very low. Further, since esters of such saturated fatty acids are solid at room temperature, the use of such saturated fatty acids for esterification purposes is not acceptable.
  • the compound of formula (A) is synthesized by customary methods by dissolving sorbitol in a solvent such as xylene, adding thereto ethylene oxide in the presence of a basic catalyst to cause an addition reaction between sorbitol and ethylene oxide, adding to that adduct an unsaturated fatty acid in an amount of from 3 to 6 moles per mole of the resulting adduct, carrying out esterification at 220° to 240°C and decolorizing and purifying the final reaction product.
  • a solvent such as xylene
  • composition of this invention consists essentially of 58 to 95% by weight of the component (I), 0.5 to 1.0% by weight of the component (II), 2.5 to 6.0% by weight of the component (III) and 2 to 35% by weight of the component (IV).
  • Compositions outside this range do not have a satisfactory emulsifying or solubilizing effect to the aforesaid vegetable oils and synthetic ester oils, and because of the poor stability of any emulsion that may be formed, the resulting emulsions are destroyed in a short time when they are allowed to stand still, resulting in phase separation.
  • the emulsifying or solubilizing agent composition of this invention is especially valuable when used for cosmetics, but it can be utilized as an emulsifier or solubilizing agent in various fields where these oils are employed, namely in the arts of foodstuffs, fiber-treating oils, detergents, metal-processing oils and the like.
  • the composition of this invention is employed in an amount of from 5 to 100 percent by weight, based on the weight of the oil component, to form oil-in-water emulsions.
  • a mixture of 20 parts of the oil component, 5 parts of the emulsifying agent composition and 75 parts of deionized water was emulsified at a temperature of 70°C, employing an agitating propeller rotation rate of 600 rpm, according to the phase inversion emulsification method.
  • the emulsifiability and stability of each emulsion were evaluated based on the following standards:
  • the state of the as-prepared emulsion was examined and observed with the naked eye and by a microscope, and the emulsifiability was evaluated by the following rating scale:
  • A bluish white emulsion of fine particles, the average particle size as measured by using the microscope being smaller than 1 ⁇
  • the invention provides mostly A grade emulsions, but some acceptable B grade emulsions can be obtained also.
  • the emulsion comprising 75 parts of the aqueous phase and 25 parts of the oil phase was allowed to stand still at 25°C for 7 days, and the ratios of separation of the emulsion into oil and aqueous phases were determined.
  • the stability was calculated from these separation ratios according to the following formula:
  • an emulsion which retains a completely emulsified state has a stability point of 0 (zero) and an emulsion which has been separated completely into an oil phase and an aqueous phase has a stability point of 20.
  • the stability point the better is the emulsion.
  • the average degree of esterification of the component (I) (the number of acyl groups as X in the formula (A)) is within the range of from 3 to 6, an excellent emulsifying effect is attained and an emulsion of good stability is obtained.
  • the average degree of esterification is 2 or lower, the emulsifying effect is low, and the stability of the resulting emulsion is bad and significant phase separation occurs.
  • Tests of the emulsification of camellia oil were conducted by using various emulsifiers (compositions) as shown in Table 2.
  • the compounding proportions were 20 parts of camellia oil, 5 parts of emulsifier composition and 75 parts of deionized water.
  • the test methods and evaluation methods were the same as described in Example 1 except that the stability was determined after the passage of 1 day and 1 week, respectively, and the emulsion was allowed to stand at 5°, 20° or 40°C.
  • Example 2 In the same manner as described in Example 2, the emulsification tests were conducted by using a mixture of 20 parts of the above synthetic ester oil, 5 parts of an emulsifier (composition) and 74 parts of deionized water. The results are shown in Table 5.
  • the degree of esterification of component (I) was 4.5
  • the component (II) was sodium oleate
  • the component (III) was oleic acid
  • the average molecular weight of component (IV) was 600. It will be noted that in comparative products 2-1 to 2-8, the proportions of the ingredients are outside the ranges of proportions of the ingredients according to the invention.
  • Comparative products 3-1 to 3-7, 4-1 to 4-5, 5-1 to 5-6, 6, 7-1 and 7-2 consisted of the components as listed in the Tables.
  • the mark (*) indicates that the emulsifiability was low, although because the viscosity of the emulsion was so high that no phase separation occurred.
  • An emulsifying agent composition comprising the following components was prepared:
  • This emulsifying agent composition was a yellowish brown liquid having a specific gravity (d 4 20 ) of 0.962, a viscosity of 172 cps as measured at 20°C, a saponification value of 118.8 and an HLB value of 8.2.
  • Components (1) and components (2) were separately heated and melted, and both the melts were mixed under vigorous agitation to form an emulsion. While the emulsion was being cooled, components (3) were added and dispersed uniformly to obtain a cream. This cream had a very good emulsion state.
  • This emulsifying agent composition was a yellowish brown liquid having a specific gravity (d 4 20 ) of 1.03, a viscosity of 321 cop as measured at 20°C, a saponification value of 82.8 and an HLB value of 11.6.
  • a milky lotion having the following composition was prepared in the same manner as described in Example 6.
  • the resulting milky lotion had a good emulsion state, and was very stable even after passage of a long time.

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Abstract

An emulsifying or solubilizing agent composition comprising 58 to 95% by weight of a surface active agent of the polyoxyethylene sorbitol-unsaturated fatty acid ester type having the formula ##EQU1## wherein the sum of n1 + n2 + n3 + n4 + n5 + n6 is from 10 to 60, and on the average, up to 3 of the X's are hydrogen and the balance of the X's are linear unsaturated acyl groups having 18 carbon atoms,
0.5 to 1.0% by weight of an alkali metal salt of a linear fatty acid having 12 to 18 carbon atoms, 2.5 to 6.0% by weight of a linear fatty acid, and 2 to 35% by weight of C18 linear unsaturated fatty acid ester of a polyethylene glycol having an average molecular weight of 150 to 2,000.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an emulsifying or solubilizing agent composition which is highly effective for emulsifying and solubilizing liquid vegetable oils and highly polar synthetic ester oils, the emulsification or solubilization of which has heretofore been regarded as being very difficult.
2. Description of the Prior Art
As emulsifiers for cosmetics, there have heretofore been used not only non-ionic surface active agents such as polyoxyethylene sorbitan-fatty acid esters, sorbitan-fatty acid esters, glycerol-fatty acid esters, polyethylene glycol-fatty acid esters and polyoxyethylenealkyl esters, but also a great variety of non-ionic, anionic, cationic and amphoteric surface active agents. In general, these emulsifiers have a good emulsifying activity to mineral oils composed of hydrocarbons and the like and animal oils such as squalane, and they provide stable emulsions of these oils. However, these surface active agents can scarcely emulsify liquid vegetable oils composed of triglycerides full of aliphatic hydrocarbon groups having unsaturated bonds (hereinafter referred to merely as "vegetable oils"), such as camellia oil and olive oil, or esters having at least one branched alkyl group, which are synthesized from a branched or linear higher fatty acid and a branched or linear higher alcohol (hereinafter referred to merely as "synthetic ester oils"), and stable emulsions of these vegetable oils or synthetic ester oils have not been provided.
SUMMARY OF THE INVENTION
We have discovered an emulsifying or solubilizing agent capable of readily emulsifying or solubilizing the aforesaid vegetable oils or synthetic ester oils to provide stable emulsions thereof. According to our invention, there is provided a composition formed by incorporating specific amounts of a fatty acid alkali metal salt, a fatty acid and an oleic acid ester of a polyethylene glycol into a polyoxyethylene sorbitol-fatty acid ester type surface active agent. More specifically, in accordance with this invention, there is provided an emulsifying or solubilizing agent composition comprising 58 to 95% by weight of a polyoxyethylene sorbitol-unsaturated fatty acid ester (hereinafter referred to as "component (I)") having the formula (A) ##EQU2## wherein the sum of n1 + n2 + n3 + n4 + n5 + n6 is from 10 to 60, and on the average up to 3 of the X's are hydrogen and the balance of the X's are linear unsaturated acyl groups having 18 carbon atoms,
0.5 to 1.0% by weight of an alkali metal salt of a linear saturated or olefinically unsaturated fatty acid having 12 to 18 carbon atoms (hereinafter referred to as "component (II)"), 2.5 to 6.0% by weight of a linear saturated or olefinically unsaturated fatty acid having 12 to 18 carbon atoms (hereinafter referred to as "component (III)"), and 2 to 35% by weight of a C18 linear unsaturated fatty acid ester of a polyethylene glycol having an average molecular weight of 150 to 2,000 (hereinafter referred to as "component (IV)").
When the above composition is used as an emulsifying or solubilizing agent, the aforesaid types of vegetable oils and synthetic ester oils, which are highly polar emollient oils and have heretofore been regarded as being difficult to emulsify, can easily be emulsified or solubilized, and good, stable and ideal emulsions of these oils can be obtained. These vegetable oils are liquid vegetable oils composed of triglycerides containing many unsaturated aliphatic hydrocarbon groups, such as camellia oil, olive oil, safflower oil, rapeseed oil, palm oil and cotton seed oil, and the synthetic ester oils are esters having at least one branched alkyl group, which are synthesized from branched or linear higher fatty acids and branched or linear higher alcohols. As such synthetic ester oil, there can be mentioned, for example, 2-heptylundecyl isostearate, glyceroltris-2-ethylhexanoate, hexadecyl-2-ethylhexanoate, hexadecyl isostearate and hexadecyl isotridecanoate. These vegetable oils and synthetic ester oils are especially useful for cosmetics, and by the use of the composition of this invention, it is possible to employ these oils in the emulsified or solubilized state in cosmetics. More specifically, it is possible to incorporate such emulsified or solubilized vegetable oils or synthetic ester oils into various cosmetic creams and lotions such as sun creams and hair creams, and to obtain cosmetics which are superior to conventional cosmetics composed mainly of mineral oils, with respect to their mild emollient effects. The composition of this invention exhibits an excellent emulsifying effect not only to these vegetable oils and synthetic ester oils, but also to mineral oils and animal oils which can also be emulsified by conventional emulsifiers.
As will be seen from the above formula (A), the polyoxyethylene sorbitol-unsaturated fatty acid ester used as the component (I) in this invention is obtained by partially or fully esterifying a sorbitol-ethylene oxide adduct with an unsaturated fatty acid having 18 carbon atoms, such as oleic acid. Among the 6 hydroxyl groups of said adduct, from 3 to 6 of such groups, on the average, are esterified. In other words, in the formula (A), from 3 to 6 of the X's are acyl groups and the remaining X's are hydrogen. (Hereinafter, the number of such acyl groups is referred to as "the degree of esterification".) When a compound having a lower degree of esterification outside the above range is employed, the emulsifying effect is diminished and good emulsions cannot be obtained. Further, the stability is reduced. Unsaturated fatty acids having 18 carbon atoms, preferably oleic acid and linoleic acid, are employed for this esterification. Thus, from 3 to 6 of the X's of the Formula (A) compound have the formula RCO--, wherein R is an olefinically unsaturated acyclic unbranched hydrocarbon radical having 17 carbon atoms and having from one to 4 double bonds in the hydrocarbon chain. If saturated fatty acids such as stearic acid and palmitic acid are employed for esterifying the sorbitolethylene oxide adduct, the emulsifying effect of compositions containing such esters is very low. Further, since esters of such saturated fatty acids are solid at room temperature, the use of such saturated fatty acids for esterification purposes is not acceptable. The compound of formula (A) is synthesized by customary methods by dissolving sorbitol in a solvent such as xylene, adding thereto ethylene oxide in the presence of a basic catalyst to cause an addition reaction between sorbitol and ethylene oxide, adding to that adduct an unsaturated fatty acid in an amount of from 3 to 6 moles per mole of the resulting adduct, carrying out esterification at 220° to 240°C and decolorizing and purifying the final reaction product.
It is critial that the composition of this invention consists essentially of 58 to 95% by weight of the component (I), 0.5 to 1.0% by weight of the component (II), 2.5 to 6.0% by weight of the component (III) and 2 to 35% by weight of the component (IV). Compositions outside this range do not have a satisfactory emulsifying or solubilizing effect to the aforesaid vegetable oils and synthetic ester oils, and because of the poor stability of any emulsion that may be formed, the resulting emulsions are destroyed in a short time when they are allowed to stand still, resulting in phase separation.
In view of the properties of the oils to which the composition of this invention is applied, the emulsifying or solubilizing agent composition of this invention is especially valuable when used for cosmetics, but it can be utilized as an emulsifier or solubilizing agent in various fields where these oils are employed, namely in the arts of foodstuffs, fiber-treating oils, detergents, metal-processing oils and the like. In general, the composition of this invention is employed in an amount of from 5 to 100 percent by weight, based on the weight of the oil component, to form oil-in-water emulsions.
This invention will now be further described in detail by reference to the following illustrative Examples. In the following examples, all references to "%" and "parts" are by weight, unless otherwise indicated.
EXAMPLE 1
Tests of the emulsification of various oils were conducted by using emulsifiers having the following compositions:
Ingredient        Compositon (%) of Emulsifier                            
______________________________________                                    
                  a        b        c                                     
Component (I)*    60.0     70.0     80.0                                  
Component (II) (sodium oleate)                                            
                  0.7      0.7      0.7                                   
Component (III) (oleic acid)                                              
                  5.0      5.0      5.0                                   
Component (IV) (average                                                   
                  34.3     24.3     14.3                                  
 molecular weight = 600)                                                  
______________________________________                                    
 *As the component (I), there were employed 7 kinds of compounds differing
 in the degree of esterification, ranging from a compound in which the    
 degree of esterification with oleic acid was 0 to a compound in which 6  
 hydroxyl groups were completely esterified. In each of these compounds th
 average mole number of the added ethylene oxide was 30.                  
Test Procedures
A mixture of 20 parts of the oil component, 5 parts of the emulsifying agent composition and 75 parts of deionized water was emulsified at a temperature of 70°C, employing an agitating propeller rotation rate of 600 rpm, according to the phase inversion emulsification method. The emulsifiability and stability of each emulsion were evaluated based on the following standards:
1. Emulsifiability:
The state of the as-prepared emulsion was examined and observed with the naked eye and by a microscope, and the emulsifiability was evaluated by the following rating scale:
A: bluish white emulsion of fine particles, the average particle size as measured by using the microscope being smaller than 1 μ
B: milky white emulsion, the average particle size as measured by using the microscope being 1 to 5 μ
C: opaque crude emulsion, the average particle size as measured by using the microscope being larger than 5 μ
In general, the invention provides mostly A grade emulsions, but some acceptable B grade emulsions can be obtained also.
2. Stability:
The emulsion comprising 75 parts of the aqueous phase and 25 parts of the oil phase was allowed to stand still at 25°C for 7 days, and the ratios of separation of the emulsion into oil and aqueous phases were determined. The stability was calculated from these separation ratios according to the following formula:
Stability Point =
(Ratio (vol %) of Separation of Oil Phase +
Ratio (vol %) of Separation of aqueous phase)
× 1/10
For example, an emulsion which retains a completely emulsified state (no phase separation) has a stability point of 0 (zero) and an emulsion which has been separated completely into an oil phase and an aqueous phase has a stability point of 20. Thus, the lowere the stability point, the better is the emulsion.
The results are shown in Table 1.
                                  Table 1                                 
__________________________________________________________________________
Emulsifier       Emulsifiability                                          
                          (Degree of Esterification in Component (I)      
Composition                                                               
       Oil       Stability                                                
                          (number of acyl groups in formula               
__________________________________________________________________________
                          (A))                                            
                          0   1   2   3   4   5   6                       
a      Olive Oil Emulsifiability                                          
                          C   C   B   A   A   A   B                       
                 Stability                                                
                          20.0                                            
                              15.0                                        
                                  12.0                                    
                                      0.0 0.0 0.0 2.5                     
       Camellia Oil                                                       
                 Emulsifiability                                          
                          C   C   B   A   A   A   B                       
                 Stability                                                
                          20.0                                            
                              15.7                                        
                                   9.7                                    
                                      0.0 0.0 0.0 2.5                     
       2-Heptylundecyl                                                    
                 Emulsifiability                                          
                          C   C   B   A   A   A   A                       
       Isostearate                                                        
                 Stability                                                
                          18.3                                            
                              15.3                                        
                                   4.3                                    
                                      0.0 0.0 0.0 0.0                     
b      Olive Oil Emulsifiability                                          
                          C   C   C   B   A   A   B                       
                 Stability                                                
                          20.0                                            
                              15.0                                        
                                  12.5                                    
                                      4.3 0.0 0.0 2.5                     
       Camellia Oil                                                       
                 Emulsifiability                                          
                          C   C   C   A   A   A   A                       
                 Stability                                                
                          20.0                                            
                              15.3                                        
                                  10.8                                    
                                      0.0 0.0 0.0 0.0                     
       2-Heptylundecyl                                                    
                 Emulsifiability                                          
                          C   C   C   A   A   A   A                       
       Isostearate                                                        
                 Stability                                                
                          20.0                                            
                              17.8                                        
                                   4.5                                    
                                      0.0 0.0 0.0 0.0                     
c      Olive Oil Emulsifiability                                          
                          C   C   C   B   A   A   A                       
                 Stability                                                
                          20.0                                            
                              20.0                                        
                                  15.7                                    
                                      10.0                                
                                          0.0 0.0 0.0                     
       Camellia Oil                                                       
                 Emulsifiability                                          
                          C   C   C   A   A   A   A                       
                 Stability                                                
                          20.0                                            
                              18.7                                        
                                  13.0                                    
                                      0.0 0.0 0.0 0.0                     
       2-Heptylundecyl                                                    
                 Emulsifiability                                          
                          C   C   C   A   A   A   A                       
       Isostearate                                                        
                 Stability                                                
                          20.0                                            
                              19.5                                        
                                   8.3                                    
                                      0.0 0.0 0.0 0.0                     
__________________________________________________________________________
As is seen from the above results, in the composition of this invention, when the average degree of esterification of the component (I) (the number of acyl groups as X in the formula (A)) is within the range of from 3 to 6, an excellent emulsifying effect is attained and an emulsion of good stability is obtained. On the other hand, when the average degree of esterification is 2 or lower, the emulsifying effect is low, and the stability of the resulting emulsion is bad and significant phase separation occurs.
EXAMPLE 2 (Emulsification of Camellia Oil)
Tests of the emulsification of camellia oil were conducted by using various emulsifiers (compositions) as shown in Table 2. The compounding proportions were 20 parts of camellia oil, 5 parts of emulsifier composition and 75 parts of deionized water. The test methods and evaluation methods were the same as described in Example 1 except that the stability was determined after the passage of 1 day and 1 week, respectively, and the emulsion was allowed to stand at 5°, 20° or 40°C.
The results are shown in Table 2.
EXAMPLE 3 (Emulsification of Olive Oil)
In the same manner as described in Example 2, emulsification tests were conducted by using a mixture of 20 parts of olive oil, 5 parts of an emulsifier (composition) and 75 parts of deionized water.
The results are shown in Table 3.
EXAMPLE 4 (Emulsification of 2-Heptylundecyl Isostearate)
In the same manner as described in Example 2, the emulsification tests were conducted by using a mixture of 20 parts of a synthetic ester oil obtained by esterification of 2-heptylundecanol with isostearic acid, 5 parts of an emulsifier (composition) and 75 parts of deionized water. The results are shown in Table 4.
EXAMPLE 5 (Emulsification of Glycerol Tris-2-ethylhexanoate
In the same manner as described in Example 2, the emulsification tests were conducted by using a mixture of 20 parts of the above synthetic ester oil, 5 parts of an emulsifier (composition) and 74 parts of deionized water. The results are shown in Table 5.
In each of the following Tables 2-5, the emulsifier products of the invention tested had the following characteristics:
                 Degree                                                   
                 of                    Average                            
Products                                                                  
        n1+n2+   Esteri-               Molecular                          
of the  n3+n4+   fication              Weight of                          
Invention                                                                 
        n5+n6    of (I)  II     III    (IV)                               
______________________________________                                    
1-1     10       3.0     sodium lauric 163                                
                         laurate                                          
                                acid                                      
1-2     20       4.0     sodium lauric 313                                
                         laurate                                          
                                acid                                      
1-3     30       4.5     sodium oleic  458                                
                         oleate acid                                      
1-4     30       4.5     sodium myristic                                  
                                       458                                
                         laurate                                          
                                acid                                      
1-5     40       4.5     sodium myristic                                  
                                       603                                
                         myristate                                        
                                acid                                      
1-6     60       5.0     sodium oleic  898                                
                         oleate acid                                      
______________________________________                                    
In the comparative products 2-1 to 2-8, the degree of esterification of component (I) was 4.5, the component (II) was sodium oleate, the component (III) was oleic acid and the average molecular weight of component (IV) was 600. It will be noted that in comparative products 2-1 to 2-8, the proportions of the ingredients are outside the ranges of proportions of the ingredients according to the invention.
Comparative products 3-1 to 3-7, 4-1 to 4-5, 5-1 to 5-6, 6, 7-1 and 7-2 consisted of the components as listed in the Tables.
In the Tables, the mark (*) indicates that the emulsifiability was low, although because the viscosity of the emulsion was so high that no phase separation occurred.
                                  Table 2                                 
__________________________________________________________________________
Results of Tests of Emulsification of Camellia Oil                        
       Composition                                                        
Invention                                                                 
       Proportion (wt.%)       HLB  Emulsion                              
Emulsifiers                                                               
       (I)   (II) (III) (IV)        Type                                  
__________________________________________________________________________
1-1    73.5  0.72 4.8   20.98  8.2  O/W                                   
1-2    85.0  0.65 4.5   9.85   9.2  O/W                                   
1-3    72.0  0.90 3.7   23.40  10.6 O/W                                   
1-4    70.0  0.70 4.2   25.10  10.3 O/W                                   
1-5    60.5  0.92 4.4   34.18  11.6 O/W                                   
1-6    75.0  0.58 3.7   20.72  13.2 O/W                                   
Comparative                                                               
Emulsifiers                                                               
2-1    70.0  0    5.0   25.0   10.3 O/W                                   
2-2    69.8  0.2  0     30.0   10.3 O/W                                   
2-3    72.0  0.2  1.4   26.4   10.3 O/W                                   
2-4    40.2  0.6  4.2   55.0   10.1 O/W                                   
2-5    20.0  0.6  2.4   77.0   10.0 O/W                                   
2-6    100.0 0    0     0      10.4 O/W                                   
2-7    0     0    0     100    9.9  O/W                                   
2-8    0     0    100   0      --   O/W                                   
3-1    POE (20) sorbitan mono- 8.0  O/W                                   
3-2    oleate/sorbitan         9.0  O/W                                   
3-3    monooleate              10.0 O/W                                   
3-4                            11.0 O/W                                   
3-5                            12.0 O/W                                   
3-6                            13.0 O/W                                   
3-7    POE (20) sorbitan       11.0 O/W                                   
       trioleate                                                          
4-1    POE (8) stearate/glycerol                                          
                               8.0  O/W                                   
4-2    monostearate            9.0  O/W                                   
4-3                            10.0 O/W                                   
4-4                            11.0 O/W                                   
4-5    POE (50) stearate/glycerol                                         
                               12.0 O/W                                   
       monostearate                                                       
4-6         "                  13.0 O/W                                   
5-1    POE (5) oleyl ether     8.8  O/W                                   
5-2    POE (5) nonylphenyl ether                                          
                               9.2  O/W                                   
5-3    POE (6) oleyl ether     10.0 O/W                                   
5-4    POE (6) stearyl ether   9.4  O/W                                   
5-5    POE (7) cetyl ether     10.7 O/W                                   
5-6    POE (9) oleyl ether     12.1 O/W                                   
6      polyoxyethylene-polyoxy-                                           
       propylene condensate    --   O/W                                   
7-1    sodium oleate           --   O/W                                   
7-2    potassium stearate      --   O/W                                   
__________________________________________________________________________
             Stability of Formed Emulsion                                 
Invention                                                                 
       Emulsi-                                                            
             after one day's                                              
                            after one week's                              
Emulsifiers                                                               
       fiability                                                          
             standing       standing                                      
__________________________________________________________________________
             5°C                                                   
                  20°C                                             
                       40°C                                        
                            5°C                                    
                                 20°C                              
                                       40°C                        
1-1    A     0    0    0    0    0    0                                   
1-2    A     0    0    0    0    0    0                                   
1-3    A     0    0    0    0    0    0                                   
1-4    A     0    0    0    0    0    0                                   
1-5    A     0    0    0    0    0    0                                   
1-6    B     0    0    0    4.5  5.2  5.2                                 
Comparative                                                               
Emulsifiers                                                               
2-1    C     2.5  2.5  3.5  9.3  9.7  10.0                                
2-2    B     0.2  0.5  0.5  12.5 12.5 12.5                                
2-3    A     0    0    0    8.0  8.0  8.3                                 
2-4    C     9.7  9.5  9.7  12.5 12.5 12.5                                
2-5    C     8.0  8.5  8.5  10.0 9.7  10.0                                
2-6    C     12.3 12.7 15.0 18.5 18.5 18.5                                
2-7    C     8.5  10.0 12.5 10.0 12.5 13.4                                
2-8    C     20.0 20.0 20.0 20.0 20.0 20.0                                
3-1    C     8.5  8.5  8.5  8.7  8.7  9.3                                 
3-2    C     8.0  8.0  8.5  8.0  8.0  8.7                                 
3-3    C     8.5  8.5  8.7  9.3  9.3  9.3                                 
3-4    C     8.7  8.7  8.7  9.3  9.3  9.3                                 
3-5    C     9.3  9.3  9.3  9.7  9.8  14.6                                
3-6    C     9.3  9.3  9.3  9.5  9.7  14.9                                
3-7    C     8.0  8.0  8.5  8.7  9.3  9.3                                 
4-1    C     0*   0*   0*   0*   0*   0*                                  
4-2    C     0*   0*   0*   0*   0*   0*                                  
4-3    C     0*   0*   2.5  0*   0*   5.3                                 
4-4    C     0*   0*   8.0  0*   0*   9.3                                 
4-5    C     0*   5.3  8.0  0*   8.7  8.0                                 
4-6    C     0*   8.0  8.8  0*   8.7  9.1                                 
5-1    C     12.5 12.5 15.0 12.5 15.0 15.0                                
5-2    C     17.0 17.5 18.5 20.0 20.0 20.0                                
5-3    C     8.0  8.7  8.7  8.0  9.3  9.3                                 
5-4    C     8.0  8.7  8.7  8.0  9.3  9.3                                 
5-5    C     6.6  7.3  10.0 6.7  7.3  10.0                                
5-6    C     10.0 17.5 19.5 10.0 18.0 20.0                                
6      C     9.3  9.3  9.3  17.5 12.5 9.3                                 
7-1    B     5.2  5.7  5.7  9.3  9.7  9.7                                 
7-2    B     5.0  5.7  5.7  10.0 8.5  10.0                                
__________________________________________________________________________
                                  Table 3                                 
__________________________________________________________________________
Results of Tests of Emulsification of Olive Oil                           
       Composition                                                        
Invention                                                                 
       Proportion (wt.%)       HLB  Emulsion                              
Emulsifiers                                                               
       (I)   (II) (III) (IV)        Type                                  
__________________________________________________________________________
1-2    85.0  0.65 4.5   9.85   9.2  O/W                                   
1-3    72.0  0.90 3.7   23.40  10.6 O/W                                   
1-4    70.0  0.70 4.2   25.10  10.3 O/W                                   
1-5    60.5  0.92 4.4   34.18  11.6 O/W                                   
Comparative                                                               
Emulsifiers                                                               
2-1    70.0  0    5.0   25.0   10.3 O/W                                   
2-2    69.8  0.2  0     30.0   10.3 O/W                                   
2-3    72.0  0.2  1.4   26.4   10.3 O/W                                   
2-4    40.2  0.6  4.2   55.0   10.1 O/W                                   
2-5    20.0  0.6  2.4   77.0   10.0 O/W                                   
2-6    100.0 0    0     0      10.4 O/W                                   
2-7    0     0    0     100    9.9  O/W                                   
2-8    0     0    100   0      --   O/W                                   
3-1    POE (20) sorbitan mono- 8.0  O/W                                   
3-2    oleate/sorbitan         9.0  O/W                                   
3-3    monooleate              10.0 O/W                                   
3-4                            11.0 O/W                                   
3-5                            12.0 O/W                                   
3-6                            13.0 O/W                                   
3-7    POE (20) sorbitan       11.0 O/W                                   
       trioleate                                                          
4-1    POE (8) stearate/glycerol                                          
                               8.0  O/W                                   
4-2    monostearate            9.0  O/W                                   
4-3                            10.0 O/W                                   
4-4                            11.0 O/W                                   
4-5    POE (50) stearate/glycerol                                         
                               12.0 O/W                                   
       monostearate                                                       
4-6           "                13.0 O/W                                   
5-1    POE (5) oleyl ether     8.8  O/W                                   
5-2    POE (5) nonylphenyl ether                                          
                               9.2  O/W                                   
5-3    POE (6) oleyl ether     10.0 O/W                                   
5-4    cetyl (6) stearyl ether 9.4  O/W                                   
5-5    POE (7) cetyl ether     10.7 O/W                                   
5-6    POE (9) oleyl ether     12.1 O/W                                   
6      polyoxyethylene-polyoxy-                                           
       propylene condensate    --   O/W                                   
7-1    sodium oleate           --   O/W                                   
7-2    potassium oleate        --   O/W                                   
__________________________________________________________________________
             Stability of Formed Emulsion                                 
Invention                                                                 
       Emulsi-                                                            
             after one day's                                              
                            after one week's                              
Emulsifiers                                                               
       fiability                                                          
             standing       standing                                      
__________________________________________________________________________
             5°C                                                   
                  20°C                                             
                       40°C                                        
                            5°C                                    
                                 20°C                              
                                      40°C                         
1-2    B     0    0    0    0    0    0                                   
1-3    A     0    0    0    0    0    0                                   
1-4    A     0    0    0    0    0    0                                   
1-5    A     0    0    0    0    0    0                                   
Comparative                                                               
Emulsifiers                                                               
2-1    C     9.5  9.7  9.7  15.0 15.0 15.0                                
2-2    B     2.5  2.7  3.2  10.0 10.0 10.0                                
2-3    B     0.2  0.2  3.0  10.0 10.0 10.0                                
2-4    C     7.3  9.5  9.5  9.3  9.5  10.0                                
2-5    C     9.5  9.5  9.5  9.7  10.0 13.0                                
2-6    C     9.5  9.5  9.5  15.0 15.0 15.0                                
2-7    C     10.0 10.0 15.0 15.0 15.0 15.0                                
2-8    C     20.0 20.0 20.0 20.0 20.0 20.0                                
3-1    C     9.0  9.0  9.0  9.3  9.3  9.3                                 
3-2    C     9.5  9.5  9.5  9.5  9.5  10.0                                
3-3    C     9.5  9.5  10.0 9.7  10.0 10.0                                
3-4    C     9.5  9.5  10.0 10.0 10.0 10.0                                
3-5    C     8.5  9.5  9.5  9.5  10.0 10.0                                
3-6    C     10.0 9.5  9.5  10.0 9.5  10.3                                
3-7    C     10.0 10.0 12.5 10.0 10.0 15.0                                
4-1    C     0*   0*   0*   0*   0*   0*                                  
4-2    C     0*   0*   0*   0*   0*   0*                                  
4-3    C     0*   0*   0*   0*   0*   0*                                  
4-4    C     0*   0.6  8.0  0*   0.6  8.0                                 
4-5    C     0*   1.0  8.0  0*   8.3  8.0                                 
4-6    C     0*   1.0  9.5  0*   8.7  9.5                                 
5-1    C     8.0  8.7  9.5  8.0  8.7  9.5                                 
5-2    C     10.0 10.0 10.0 15.0 15.0 20.0                                
5-3    C     8.0  9.5  9.5  8.7  10.0 10.0                                
5-4    C     0*   0*   0*   0*   0*   0*                                  
5-5    C     6.7  6.7  9.5  6.7  7.5  10.0                                
5-6    C     9.5  9.5  9.5  10.0 10.0 10.0                                
6      C     9.5  10.0 10.0 10.0 15.0 15.0                                
7-1    B     0.2  0.2  0.5  10.0 10.0 10.0                                
7-2    B     0.2  0.2  0.5  10.0 10.0 10.0                                
__________________________________________________________________________
                                  Table 4                                 
__________________________________________________________________________
Results of Tests of Emulsification of 2-Heptylundecyl Isostearate         
       Composition                                                        
Invention                                                                 
       Proportion (wt.%)       HLB  Emulsion                              
Emulsifiers                                                               
       (I)   (II) (III) (IV)        Type                                  
__________________________________________________________________________
1-1    73.5  0.72 4.8   20.98  8.2  O/W                                   
1-2    85.0  0.65 4.5   9.85   9.2  O/W                                   
1-3    72.0  0.90 3.7   23.40  10.6 O/W                                   
1-4    70.0  0.70 4.2   25.10  10.3 O/W                                   
1-5    60.5  0.92 4.4   34.18  11.6 O/W                                   
1-6    75.0  0.58 3.7   20.72  13.2 O/W                                   
Comparative                                                               
Emulsifiers                                                               
2-1    70.0  0    5.0   25.0   10.3 O/W                                   
2-2    69.8  0.2  0     30.0   10.3 O/W                                   
2-3    72.0  0.2  1.4   26.4   10.3 O/W                                   
2-4    40.2  0.6  4.2   55.0   10.1 O/W                                   
2-5    20.0  0.6  2.4   77.0   10.0 O/W                                   
2-6    100.0 0    0     0      10.4 O/W                                   
2-7    0     0    0     100    9.9  O/W                                   
2-8    0     0    100   0      --   O/W                                   
3-1    POE (20) sorbitan mono- 8.0  O/W                                   
3-2    oleate/sorbitan         9.0  O/W                                   
3-3    monooleate              10.0 O/W                                   
3-4                            11.0 O/W                                   
3-5                            12.0 O/W                                   
3-6                            13.0 O/W                                   
3-7    POE (20) sorbitan       11.0 O/W                                   
       trioleate                                                          
4-1    POE (8) stearate/glycerol                                          
                               8.0  O/W                                   
4-2    monostearate            9.0  O/W                                   
4-3                            10.0 O/W                                   
4-4                            11.0 O/W                                   
4-5    POE (50) stearate/glycerol                                         
                               12.0 O/W                                   
       monostearate                                                       
4-6         "                  13.0 O/W                                   
5-1    POE (5) oleyl ether     8.8  O/W                                   
5-2    POE (5) nonylphenyl ether                                          
                               9.2  O/W                                   
5-3    POE (6) oleyl ether     10.0 O/W                                   
5-4    POE (6) stearyl ether   9.4  O/W                                   
5-5    POE (7) cetyl ether     10.7 O/W                                   
5-6    POE (9) oleyl ether     12.1 O/W                                   
6      polyoxyethylene-polyoxy-                                           
                               --   O/W                                   
       propylene                                                          
7-1    sodium oleate           --   O/W                                   
7-2    potassium oleate        --   O/W                                   
__________________________________________________________________________
             Stability of Formed Emulsion                                 
Invention                                                                 
       Emulsi-                                                            
             after one day's                                              
                            after one week's                              
Emulsifiers                                                               
       fiability                                                          
             standing       standing                                      
__________________________________________________________________________
             5°C                                                   
                  20°C                                             
                       40°C                                        
                            5°C                                    
                                 20°C                              
                                      40°C                         
1-1    B     0    0    0    0.2  0.3  0.5                                 
1-2    A     0    0    0    0    0    0                                   
1-3    A     0    0    0    0    0    0                                   
1-4    A     0    0    0    0    0    0                                   
1-5    A     0    0    0    0    0    0                                   
1-6    B     0    0    0    0    0    0                                   
Comparative                                                               
Emulsifiers                                                               
2-1    C     3.5  4.7  5.5  6.7  9.3  9.3                                 
2-2    C     4.5  5.0  6.0  8.5  8.0  8.5                                 
2-3    B     0.2  0.2  0.3  8.7  8.7  9.3                                 
2-4    B     2.2  2.5  2.0  8.7  9.0  9.3                                 
2-5    C     8.3  8.3  8.7  10.0 10.2 15.0                                
2-6    C     8.7  9.0  9.3  10.0 10.0 10.0                                
2-7    C     12.5 12.5 14.0 13.8 14.2 15.0                                
2-8    C     20.0 20.0 20.0 20.0 20.0 20.0                                
3-1    C     0*   0*   0*   0*   0*   0.1                                 
3-2    B     0    0    0    0.1  0.1  0.6                                 
3-3    A     0    0    0    0.2  0.2  0.6                                 
3-4    C     0    0    0    8.9  8.9  9.3                                 
3-5    C     8.7  9.9  10.4 10.4 10.4 10.7                                
3-6    C     8.9  8.9  8.9  10.4 10.7 10.7                                
3-7    C     0    0    0    0.2  0.6  0.7                                 
4-1    C     0*   0*   0*   0*   0*   0*                                  
4-2    C     0*   0*   0*   0*   0*   0*                                  
4-3    C     0*   0*   0*   0*   0*   0*                                  
4-4    C     0*   0*   0*   0*   0.7  2.1                                 
4-5    C     0*   0*   0*   1.1  2.1  1.1                                 
4-6    C     0*   0*   0*   4.7  5.4  8.1                                 
5-1    C     8.1  9.5  9.7  9.7  9.5  9.7                                 
5-2    C     8.7  12.5 13.5 14.5 14.5 15.0                                
5-3    C     0    0    0    4.5  5.4  9.1                                 
5-4    C     0    0    0    8.7  9.3  9.3                                 
5-5    C     6.7  8.0  8.7  6.7  8.1  8.9                                 
5-6    C     7.3  9.1  10.0 7.3  9.3  10.1                                
6      C     10.0 12.5 14.5 17.0 17.5 17.5                                
7-1    C     6.2  4.0  10.0 9.3  8.0  12.5                                
7-2    C     5.7  4.2  10.0 9.7  8.5  12.5                                
__________________________________________________________________________
                                  Table 5                                 
__________________________________________________________________________
Results of Tests of Emulsification of Glycerol Tris-2-ethyl-hexanoate     
       Composition                                                        
Invention                                                                 
       Proportion (wt.%)       HLB  Emulsion                              
Emulsifiers                                                               
       (I)   (II) (III) (IV)        Type                                  
__________________________________________________________________________
1-1    73.5  0.72 4.8   20.98  8.2  O/W                                   
1-2    85.0  0.65 4.5   9.85   9.2  O/W                                   
1-3    72.0  0.90 3.7   23.40  10.6 O/W                                   
1-4    70.0  0.70 4.2   25.10  10.3 O/W                                   
1-5    60.5  0.92 4.4   34.18  11.6 O/W                                   
1-6    75.0  0.58 3.7   20.72  13.2 O/W                                   
Comparative                                                               
Emulsifiers                                                               
2-1    70.0  0    5.0   25.0   10.3 O/W                                   
2-2    69.8  0.2  0     30.0   10.3 O/W                                   
2-3    72.0  0.2  1.4   26.4   10.3 O/W                                   
2-4    4.2   0.6  4.2   55.0   10.1 O/W                                   
2-5    20.0  0.6  2.4   77.0   10.0 O/W                                   
2-6    100.0 0    0     0      10.4 O/W                                   
2-7    0     0    0     100    9.9  O/W                                   
2-8    0     0    100   0      --   O/W                                   
3-1    POE (20) sorbitan mono- 8.0  O/W                                   
3-2    oleate/sorbitan         9.0  O/W                                   
3-3    monooleate              10.0 O/W                                   
3-4                            11.0 O/W                                   
3-5                            12.0 O/W                                   
3-6                            13.0 O/W                                   
3-7    POE (20) sorbitan       11.0 O/W                                   
       trioleate                                                          
4-1    POE (8) stearate/glycerol                                          
                               8.0  O/W                                   
4-2    monostearate            9.0  O/W                                   
4-3                            10.0 O/W                                   
4-4                            11.0 O/W                                   
4-5    POE (50) stearate/glycerol                                         
                               12.0 O/W                                   
       monostearate                                                       
4-6         "                  13.0 O/W                                   
5-1    POE (5) oleyl ether     8.8  O/W                                   
5-2    POE (5) nonylphenyl ether                                          
                               9.2  O/W                                   
5-3    POE (6) oleyl ether     10.0 O/W                                   
5-4    POE (6) stearyl ether   9.4  O/W                                   
5-5    POE (7) cetyl ether     10.7 O/W                                   
5-6    POE (9) oleyl ether     12.1 O/W                                   
6      polyoxyethylene-polyoxy-                                           
                               --   O/W                                   
       propylene condensate                                               
7-1    sodium oleate           --   O/W                                   
7-2    potassium oleate        --   O/W                                   
__________________________________________________________________________
             Stability of Formed Emulsion                                 
Invention                                                                 
       Emulsi-                                                            
             after one day's                                              
                            after one week's                              
Emulsifiers                                                               
       fiability                                                          
             standing       standing                                      
__________________________________________________________________________
             5°C                                                   
                  20°C                                             
                       40°C                                        
                            5°C                                    
                                 20°C                              
                                      40°C                         
1-1    A     0    0    0    0    0    0                                   
1-2    A     0    0    0    0    0    0                                   
1-3    A     0    0    0    0    0    0                                   
1-4    A     0    0    0    0    0    0                                   
1-5    A     0    0    0    0    0    0                                   
1-6    A     0    0    0    0    0.2  2.1                                 
Comparative                                                               
Emulsifiers                                                               
2-1    C     4.5  4.7  4.7  8.5  9.2  9.5                                 
2-2    C     4.5  4.9  5.3  8.0  9.7  10.0                                
2-3    B     0.2  0.2  0.2  0.8  1.0  1.0                                 
2-4    C     8.0  8.7  8.9  9.3  9.3  9.5                                 
2-5    C     9.3  9.5  9.5  9.7  10.0 12.0                                
2-6    C     7.7  8.0  8.7  8.7  9.3  10.0                                
2-7    C     8.7  9.5  12.5 12.5 14.7 15.0                                
2-8    C     20.0 20.0 20.0 20.0 20.0 20.0                                
3-1    A     0    0    0    0.2  0.2  0.2                                 
3-2    B     0    0    0    0.2  0.2  0.2                                 
3-3    C     0    0    0    0.2  0.2  0.2                                 
3-4    C     0    0    0    0.2  5.4  10.0                                
3-5    C     0    0    8.5  9.7  9.6  9.3                                 
3-6    C     0    2.5  8.5  8.4  9.3  8.9                                 
3-7    C     0    9.7  9.7  9.3  9.7  10.0                                
4-1    C     0*   0*   0*   0*   0*   0*                                  
4-2    C     0*   0*   0*   0*   0*   0*                                  
4-3    C     0*   0*   0*   0*   0*   0*                                  
4-4    C     0*   8.5  9.5  0*   8.7  9.3                                 
4-5    C     0*   8.5  9.5  0*   8.7  9.7                                 
4-6    C     0*   8.5  8.5  0*   10.0 9.6                                 
5-1    C     8.7  9.5  9.7  8.7  10.0 10.0                                
5-2    C     12.5 13.5 12.0 14.3 20.0 20.0                                
5-3    C     6.7  8.0  6.7  6.0  8.3  7.3                                 
5-4    C     0*   0*   0*   0.8  1.0  2.5                                 
5-5    C     6.7  8.3  9.0  6.7  8.3  9.6                                 
5-6    C     0    0    0    2.0  2.0  2.7                                 
6      C     10.0 10.5 12.0 10.0 10.5 12.0                                
7-1    B     0    0.2  0.2  0.4  2.0  2.1                                 
7-2    B     0    0.2  0.2  0.4  2.0  2.7                                 
__________________________________________________________________________
As is seen from the results obtained in Examples 2 to 5, although vegetable oils or synthetic ester oils cannot be emulsified at all or can be emulsified only insufficiently by conventional known emulsifiers, they can easily be emulsified by the emulsifying agent composition of this invention and good emulsions having an excellent stability can be obtained. It is also seen that even if the same components as in this invention are used, if the proportion of these components is outside the ranges specified in this invention, no satisfactory emulsifying effect can be attained and the stability of the resulting emulsion is poor.
EXAMPLE 6 (O/W Cream)
An emulsifying agent composition comprising the following components was prepared:
(I)   polyoxyethylene (P=10) sorbitol                                     
                               73.5%                                      
      oleate (average degree of ester-                                    
      ification = 3.0)                                                    
(II)  sodium oleate            0.72%                                      
(III) oleic acid               4.8%                                       
(IV)  polyethylene glycol oleate                                          
                               20.98%                                     
      (average molecular weight = 200)                                    
This emulsifying agent composition was a yellowish brown liquid having a specific gravity (d4 20) of 0.962, a viscosity of 172 cps as measured at 20°C, a saponification value of 118.8 and an HLB value of 8.2.
by using this emulsifying agent composition, an O/W type cream having the following composition was prepared:
(1)    camellia oil       25 parts                                        
       bees wax            5 parts                                        
       paraffin wax        5 parts                                        
       vaseline            7 parts                                        
       emulsifying agent compo-                                           
                           6 parts                                        
       sition                                                             
(2)    glycerin            5 parts                                        
       water              47 parts                                        
(3)    perfume, preservative                                              
                          suitable amounts                                
Components (1) and components (2) were separately heated and melted, and both the melts were mixed under vigorous agitation to form an emulsion. While the emulsion was being cooled, components (3) were added and dispersed uniformly to obtain a cream. This cream had a very good emulsion state.
EXAMPLE 7 (Milky Lotion)
An emulsifying agent having the following components was prepared:
(1)   polyoxyethylene (P=40) sorbitol oleate                              
                                60.5%                                     
      (average degree of esterification = 4.5)                            
(II)  sodium oleate             0.92%                                     
(III) oleic acid                4.4%                                      
(IV)  polyethylene glycol oleate                                          
                                34.18%                                    
      (average molecular weight = 800)                                    
This emulsifying agent composition was a yellowish brown liquid having a specific gravity (d4 20) of 1.03, a viscosity of 321 cop as measured at 20°C, a saponification value of 82.8 and an HLB value of 11.6.
By using this emulsifying agent composition, a milky lotion having the following composition was prepared in the same manner as described in Example 6.
______________________________________                                    
(1)   olive oil            30      parts                                  
      bees wax             2       parts                                  
      paraffin wax         2       parts                                  
      cetyl alcohol        1       part                                   
      emulsifying agent composition                                       
                           5       parts                                  
(2)   glycerin             5       parts                                  
      water                55      parts                                  
(3)   perfume, preservatives                                              
______________________________________                                    
The resulting milky lotion had a good emulsion state, and was very stable even after passage of a long time.

Claims (10)

The embodiments of the invention in which an exclusive property or privelege is claimed are defined as follows:
1. An emulsifying or solubilizing composition, consisting essentially of
I. from 58 to 95 percent by weight of a surface active agent having the formula ##EQU3## wherein the sum of n1 to n6 is from 10 to 60 and, on the average, up to 3 of the X's are hydrogen and the balance of the X's are linear unsaturated acyl groups having 18 carbon atoms,
Ii. from 0.5 to 1.0 percent by weight of an alkali metal salt of a linear fatty acid having 12 to 18 carbon atoms,
Iii. from 2.5 to 6.0 percent by weight of a linear fatty acid having 12 to 18 carbon atoms, and
Iv. from 2 to 35 percent by weight of a C18 linear unsaturated fatty acid ester of polyethylene glycol having an average molecular weight of 150 to 2000.
2. A composition as claimed in claim 1 in which ingredient II is sodium oleate and ingredient III is oleic acid.
3. A composition as claimed in claim 1 in which ingredient II is sodium laurate and ingredient III is lauric acid.
4. A composition as claimed in claim 1 in which ingredient II is sodium laurate and ingredient III is myristic acid.
5. A composition as claimed in claim 1 in which ingredient II is sodium myristate and ingredient III is myristic acid.
6. A composition as claimed in claim 1, containing from about 60 to 80 percent by weight of ingredient I.
7. An oil-in-water emulsion containing as an emulsifier for the oil phase, from 5 to 100 percent by weight, based on the weight of the oil components, of a composition as claimed in claim 1.
8. An emulsion as claimed in claim 7, in which said oil component consists of a liquid vegetable oil consisting essentially of triglycides containing several unsaturated aliphatic hydrocarbon groups or synthetic ester oils having at least one branched alkyl group obtained by reacting a branched or linear higher fatty acid with a branched or linear higher alcohol.
9. An emulsion as claimed in claim 7 in which the oil component is selected from the group consisting of camellia oil, olive oil, safflower oil, rapeseed oil, palm oil and cotton seed oil.
10. An emulsion as claimed in claim 7 in which the oil component is selected from the group consisting of 2-heptylundecyl isostearate, glycerol-tris-2-ethylhexanoate, hexadecyl-2-ethylhexanoate, hexadecyl isostearate and hexadecyl isotridecanoate.
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Cited By (13)

* Cited by examiner, † Cited by third party
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US4097403A (en) * 1976-02-05 1978-06-27 Kao Soap Co., Ltd. Oil-in-water emulsion and emulsifying or solubilizing agent composition useful therein
EP0007737A1 (en) * 1978-07-31 1980-02-06 Atlas Chemical Industries (U.K.) Ltd An aqueous solution containing a surfactant and its uses in emulsification
FR2443873A1 (en) * 1978-12-14 1980-07-11 Kao Corp NOVEL EMULSIFYING COMPOSITION FOR THE PRODUCTION AND STABILIZATION OF WATER-IN-OIL EMULSIONS
US4454113A (en) * 1982-09-21 1984-06-12 Scm Corporation Stabilization of oil and water emulsions using polyglycerol esters of fatty acids
US4608057A (en) * 1985-06-03 1986-08-26 Texaco Inc. Clear stable motor fuel composition
EP0399377A1 (en) * 1989-05-19 1990-11-28 Nihon Parkerizing Co., Ltd. Cold rolling oil for steel sheet
US4996004A (en) * 1982-08-14 1991-02-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US5059347A (en) * 1989-03-17 1991-10-22 Ciba-Geigy Corporation Aqueous antioxident emulsions
US5116536A (en) * 1982-08-14 1992-05-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US5192462A (en) * 1989-03-21 1993-03-09 Croda Inc. Thickening agents for topical preparations
WO2005059042A3 (en) * 2003-12-17 2005-11-03 Ici Plc Surfactant
CN101448873B (en) * 2006-05-19 2012-07-18 陶氏康宁东丽株式会社 Polyether and method for producing the same
US11547137B2 (en) * 2015-03-10 2023-01-10 Givaudan Sa Topical flavouring compositions comprising oleic acid and sodium oleate

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JPS57197204A (en) * 1981-05-27 1982-12-03 Shiseido Co Ltd Emulsion cosmetic
JP5362179B2 (en) * 2006-10-20 2013-12-11 日清オイリオグループ株式会社 Polyoxyethylene sorbitol fatty acid ester and aqueous wax dispersion containing the same
JP7788083B2 (en) 2020-12-28 2025-12-18 大日本印刷株式会社 Organic device, mask group, mask, and method for manufacturing organic device
JP7788084B2 (en) 2020-12-28 2025-12-18 大日本印刷株式会社 Organic device, mask group, mask, and method for manufacturing organic device
KR20220169923A (en) 2021-06-21 2022-12-28 다이니폰 인사츠 가부시키가이샤 Manufacturing method of mask and mask
US20220406853A1 (en) 2021-06-21 2022-12-22 Dai Nippon Printing Co., Ltd. Organic device, group of masks, mask, and manufacturing method for organic device

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US2269529A (en) * 1940-06-15 1942-01-13 Harry Bennett Emulsifier and emulsion
US2786013A (en) * 1953-07-06 1957-03-19 Atlas Powder Co Emulsifier compositions and insecticidal emulsions
US3634285A (en) * 1969-03-24 1972-01-11 Stauffer Wacker Silicone Corp Silicone release emulsion
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097403A (en) * 1976-02-05 1978-06-27 Kao Soap Co., Ltd. Oil-in-water emulsion and emulsifying or solubilizing agent composition useful therein
EP0007737A1 (en) * 1978-07-31 1980-02-06 Atlas Chemical Industries (U.K.) Ltd An aqueous solution containing a surfactant and its uses in emulsification
FR2443873A1 (en) * 1978-12-14 1980-07-11 Kao Corp NOVEL EMULSIFYING COMPOSITION FOR THE PRODUCTION AND STABILIZATION OF WATER-IN-OIL EMULSIONS
US4312777A (en) * 1978-12-14 1982-01-26 Kao Soap Co., Ltd. Emulsifier composition
US5116536A (en) * 1982-08-14 1992-05-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US4996004A (en) * 1982-08-14 1991-02-26 Bayer Aktiengesellschaft Preparation of pharmaceutical or cosmetic dispersions
US4454113A (en) * 1982-09-21 1984-06-12 Scm Corporation Stabilization of oil and water emulsions using polyglycerol esters of fatty acids
US4608057A (en) * 1985-06-03 1986-08-26 Texaco Inc. Clear stable motor fuel composition
US5059347A (en) * 1989-03-17 1991-10-22 Ciba-Geigy Corporation Aqueous antioxident emulsions
US5192462A (en) * 1989-03-21 1993-03-09 Croda Inc. Thickening agents for topical preparations
EP0399377A1 (en) * 1989-05-19 1990-11-28 Nihon Parkerizing Co., Ltd. Cold rolling oil for steel sheet
WO2005059042A3 (en) * 2003-12-17 2005-11-03 Ici Plc Surfactant
US20070299228A1 (en) * 2003-12-17 2007-12-27 Imperial Chemical Industries Plc Surfactant
US8883945B2 (en) 2003-12-17 2014-11-11 Croda International Plc Surfactant
CN101448873B (en) * 2006-05-19 2012-07-18 陶氏康宁东丽株式会社 Polyether and method for producing the same
US11547137B2 (en) * 2015-03-10 2023-01-10 Givaudan Sa Topical flavouring compositions comprising oleic acid and sodium oleate

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